Ink-jet ink comprising cross-linked pigment dispersion and a polymeric binder

ABSTRACT

The present disclosure provides an ink-jet ink containing an aqueous ink vehicle, an aqueous dispersion and a polymeric binder. The aqueous dispersion contains a colorant and a polyurethane dispersant, wherein the polyurethane dispersant is made with a polymer having cross-linkable moieties that are cross-linked with a cross-linking agent.

BACKGROUND OF THE INVENTION

This application claims priority under 35 U.S.C. §119 from U.S.Provisional Application Ser. No. 61/378,529, filed Aug. 31, 2010.

This disclosure relates to novel aqueous Inkjet inks containing anaqueous vehicle, an aqueous dispersion and a polymeric binder. Theaqueous dispersion contains a colorant and a polyurethane dispersantwith cross-linkable moieties that are cross-linked with a cross-linkingagent.

Aqueous dispersions of pigment particles are widely used in ink-jetprinting. Because a pigment is typically not soluble in an aqueousvehicle, it is often required to use a dispersing agent, such as apolymeric dispersant or a surfactant, to produce a stable dispersion ofthe pigment in the aqueous vehicle. However, because the pigment isdispersed in a liquid vehicle, there is a tendency for pigment particlesto agglomerate or flocculate while the ink is being stored or while theink is being used, for example, being printed.

There has been effort in the art directed at improving the stability ofpigment dispersions. The effort to improve dispersion stability to datehas included improvements in the processes used to make the dispersions,the development of new dispersants and the exploration of theinteraction between dispersants and pigment particles, and betweendispersants and aqueous vehicle. While much of the effort has generalapplication at improving dispersion stability, some of that effort hasnot found utility in particular applications. For example, the pigmentdispersions used in ink-jet printing applications have very unique anddemanding requirements. It is critical that ink components comprisingpigment dispersion remain stable, not only in storage but also overrepeated jetting cycles. It is also desirable that the pigmentdispersions offer good durability, good rub-fastness, wet-fastness andhighlighter pen fastness.

A need exists for highly stable, higher-quality, better smudge andhighlighter smear inks for ink-jet applications. The present inventionsatisfies this need by providing an ink containing a binder and across-finked pigment dispersion based on a polyurethane dispersanthaving cross-linkable moieties both pendent to the polymer backbone andterminal to the polymer chain, and the cross-linking of these moietieswith a cross-linking agent.

SUMMARY OF THE INVENTION

An embodiment of the invention provides an ink-jet ink comprising anaqueous ink vehicle, an aqueous pigment dispersion and a polymericbinder, wherein the aqueous pigment dispersion comprises a colorant anda polyurethane dispersant, and the polymeric binder is non-reactive tothe colorant, and wherein the polyurethane dispersant is comprised of apolymer with:

-   -   (a) an aqueous dispersing moiety, and    -   (b) a cross-linkable moiety that is cross-linked with a        cross-linking agent, wherein the cross-linkable moiety is        pendent to the polymer backbone and terminal to the polymer        chain; wherein the polyurethane dispersant comprises at least        one compound of the general structure of Formula I:

-   -   wherein each X is independently OH, SH, COOH or NHR⁴;    -   each Y is independently O, S or NR⁴;    -   each W is N, O or S:    -   each R¹ is independently C₁-C₂₀ alkyl, C₃-C₂₀ substituted alkyl,        C₆-C₄₀ aryl or C₉-C₄₀ substituted aryl;    -   R² is comprised of difunctional isocyanate reactants Z¹, Z² and        Z³, wherein there is at least one Z¹, at least one Z² and at        least one Z³;    -   each R³ is independently C₁-C₂₀ alkyl or C₃-C₂₀ substituted        alkyl;    -   each R⁴ is independently —R³—X, H, C₁-C₂₀ alkyl or C₃-C₂₀        substituted alkyl;    -   n is an integer from 2 to 30;    -   Z¹ is a difunctional isocyanate reactant substituted with an        aqueous dispersing moiety;    -   Z² is a difunctional isocyanate reactant substituted with one or        more cross-linkable moieties; and    -   Z³ is a polyol with MW less than 3000.

Another embodiment provides that the polymeric binder is one or moremembers selected from the group consisting of polyurethane, acrylics,styrene acrylics, styrene butadienes, styrene butadiene acrylonitriles,neoprenes, ethylene acrylic acid copolymer, ethylene vinyl acetate, andmixtures thereof.

Another embodiment provides that the cross-linking agent is one or moremembers selected from the group consisting of epoxide, isocyanate,carbodiimide, N-methylol, oxazoline, silane, and mixtures thereof.

Another embodiment provides that Z¹ is a polyol substituted with theaqueous dispersing moiety.

Another embodiment provides that Z² is a polyol substituted with one ormore cross-linkable moieties.

Another embodiment provides that the aqueous dispersing moiety consistsof one or more carboxyl groups.

Another embodiment provides that the cross-linkable moiety consists ofone or more carboxyl groups.

Another embodiment provides that Y is NR⁴.

Another embodiment provides that the polymeric binder is polyurethane.

Another embodiment provides that X is OH.

Another embodiment provides that X is NHR⁴.

Another embodiment provides that R⁴ is —R³—X and the polymeric binder ispolyurethane.

Another embodiment provides that each W is O.

Another embodiment provides that each W is N.

Yet another embodiment provides that the mole ratio of thecross-linkable moiety to the cross-linking agent is from 15:1 to 1:1.5.

These and other features and advantages of the present invention will bemore readily understood by those of ordinary skill in the art from areading of the following Detailed Description. Certain features of theinvention which are, for clarity, described above and below as aseparate embodiment, may also be provided in combination in a singleembodiment. Conversely, various features of the invention that aredescribed in the context of a single embodiment, may also be provided,separately or in any subcombination.

DETAILED DESCRIPTION

Unless otherwise stated or defined, all technical and scientific termsused, herein have commonly understood meanings by one of ordinary skillin the art to which this invention pertains.

Unless stated otherwise, all percentages, parts, ratios, etc., are byweight.

When an amount, concentration, or other value or parameter is given aseither a range, preferred range or a list of upper preferable values andlower preferable values, this is to be understood as specificallydisclosing all ranges formed, from any pair of any upper range limit orpreferred value and any lower range limit or preferred value, regardlessof whether ranges are separately disclosed. Where a range of numericalvalues is recited herein, unless otherwise stated, the range is intendedto include the endpoints thereof, and all integers and fractions withinthe range.

When the term “about” is used in describing a value or an end-point of arange, the disclosure should be understood to include the specific valueor end-point referred to.

As used herein, “comprising” is to be interpreted as specifying thepresence of the stated features, integers, steps, or components asreferred to, but does not preclude the presence or addition of one ormore features, integers, steps, or components, or groups thereof.Additionally, the term “comprising” is intended to include examplesencompassed by the terms “consisting essentially of” and “consistingof.” Similarly, the term “consisting essentially of” is intended toinclude examples encompassed by the term “consisting of.”

As used herein, the dispersions produced with the polyurethane describedabove can be utilized to disperse particles, especially pigments forink-jet inks. These inks can be printed on all normally used ink-jetsubstrates including textile substrates.

As used herein, the term “dispersion” means a two phase system where onephase consists of finely divided particles (often in the colloidal sizerange) distributed throughout a bulk substance, of the particles beingthe dispersed or internal phase and the bulk substance being thecontinuous or external phase.

As used herein, the term “dispersant” means a surface active agent addedto a suspending medium to promote uniform and maximum separation ofextremely fine solid, particles often of colloidal size. For pigments,dispersants are most often polymeric dispersants. The polyurethanedispersants described herein are in fact dispersions themselves.

As used herein, the term “OD” means optical density.

As used herein, the term “aqueous vehicle” refers to water or a mixtureof water and at least one water-soluble, or partially water-soluble(i.e. methyl ethyl ketone), organic solvent (co-solvent).

As used herein, the tem “ionizable groups,” means potentially ionicgroups.

As used herein, the term “substantially” means being of considerabledegree, almost all.

As used herein, the term “MW” means weight average molecular weight.

As used herein, the term “D50” means the volume particle diameter of the50th percentile (median) of the distribution of particle sizes.

As used herein, the term ‘D95’ means the volume particle diameter of the95th percentile of the distribution of particle sizes.

As used herein, the term “pendent” means that a substituent is directlyattached to the backbone of a polymer or via a linkage of 1 to 10 atoms.

As used herein, the term “NCO” means isocyanate.

As used herein, the term “cPs” means centipoise, a viscosity unit.

As used herein, the term “mN.m⁻¹” means milliNewtons per meter, asurface tension unit.

As used herein, the term “mPa·s” means millipascal second, a viscosityunit.

As used herein, the term “prepolymer” means the polymer that is anintermediate in a polymerization process, and can be considered apolymer.

As used herein, the term “AN” means acid number, mg KOH/gram of solidpolymer.

As used herein, the term “PUD” means the polyurethanes dispersionsdescribed herein.

As used herein, the term “BMEA” means bis(methoxyethyl)amine.

As used herein, the term “DBTDL” means dibutyltin dilaurate.

As used herein, the term “DEA” means diethanolamine.

As used herein, the term “DMPA” means dimethylol propionic acid.

As used herein, the term “HDI” means 1,6-hexamethylene diisocyanate.

As used herein, the term “IPDI” means isophorone diisocyanate.

As used herein, the term “TMDI” means trimethylhexamethylenediisocyanate.

As used herein, the term “TMXDI” means m-tetramethylene xylylenediisocyanate.

As used herein, the term “NMP” means n-Methyl pyrolidone.

As used herein, the term “TDI” means 2,4-toluene diisocyanate.

As used herein, the term “MDI” means 4,4′-diphenylmethane diisocyanate.

As used herein, the term “H₁₂MDI” means 4,4′-dicyclohexylmethanediisocyanate.

As used herein, the term “TODI” means 3,3′-dimethyl-4,4′-biphenyldiisocyanate.

As used herein, the term “C₁₂DI” means dodecane diisocyanate.

As used herein, the term “NDI” means 1,5-naphthalene diisocyanate.

As used herein, the term “IPDI” means isophorone diisocyanate.

As used herein, the term “TEB” means triethylene glycol monobutyl ether,a reagent supplied by Dow Chemical.

As used herein, the term “Sulfolane” means tetramethylene sulfone.

As used herein, the term “TRB-2” means Dainichiseika® TRB-2, a cyanpigment.

As used herein, Terathane® 650 is a polyether diol from Invista,Wichita, Kans.

As used herein, Etemacoll® UH-50 is a polycarbonate diol from UBEIndustries, Tokyo, Japan.

As used herein, Denacol® 321 is trimethylolpropane polyglycidyl ether, across-linking reagent from Nagase Chemicals Ltd., Osaka, Japan,

Unless otherwise noted, the above chemicals were obtained from Aldrich(Milwaukee, Wis.) or other similar suppliers of laboratory chemicals.

In addition, references in the singular may also include the plural (forexample, “a” and “an” may refer to one, or one or more) unless thecontext specifically states otherwise.

Polyurethane Dispersants

Polyurethane polymers are, for the purposes of the present disclosure,polymers wherein the polymer backbone contains urethane linkage derivedfrom the reaction of an isocyanate group (from, e.g., a di- orhigher-functional monomeric, oligomeric or polymeric polyisocyanate)with a hydroxyl group (from, e.g., a di- or higher-functional monomeric,oligomeric or polymeric polyol). Such polymers may, in addition to theurethane linkage, also contain other isocyanate-derived linkages such asurea, as well as other types of linkages present in the polyisocyanatecomponents or polyol components (such as, for example, ester and etherlinkage).

The polyurethane dispersant of the present invention comprises at leastone compound of the general structure of Formula I:

wherein each X is independently OH, SH, COOH or NHR⁴;

each Y is independently O, S or NR⁴;

each W is N, O or S;

each R¹ is independently C₁-C₂₀ alkyl, C₃-C₂₀ substituted alkyl, C₆-C₄₀aryl or C₉-C₄₀ substituted aryl;

R² is comprised of difunctional isocyanate reactants Z¹, Z² and Z³,wherein there is at least one Z¹, at least one Z² and at least one Z³;

each R³ is independently C₁-C₂₀ alkyl or C₃-C₂₀ substituted alkyl;

each R⁴ is independently —R³—X, H, C₁-C²⁰ alkyl or C₃-C₂₀ substitutedalkyl;

n is an integer from 2 to 30;

Z¹ is a difunctional isocyanate reactant substituted with an aqueousdispersing moiety;

Z² is a difunctional isocyanate reactant substituted with one or morecross-linkable moieties; and

Z³ is a polyol with MW less than 3000.

The key features of the polyurethane dispersant are the cross-linkablemoieties that are pendent to the polymer backbone and terminal to thepolymer chain. The term “pendent” means that a substituent is directlyattached, to the backbone of a polymer or via a linkage of between 1 to10 atoms. Typically, the cross-linkable moieties that are pendent to thepolymer backbone reside in the R² group of Formula I. Specifically theZ² component in R² is a polyol substituted with one or morecross-linkable moieties. Typically these cross-linkable moieties arecarboxyl, hydroxyl, amino or mecapto groups. The cross-linkable moietiesthat are terminal to the polymer chain are represented by the X group inFormula I, These cross-linkable moieties, upon reacting with across-linking agent, provide a cross-linked pigment dispersion havingsuperior properties.

The R² group in Formula I is comprised, of difunctional isocyanatereactants Z¹, Z²and Z³, wherein there is at least one Z¹, at least oneZ² and at least one Z³. This R² group provides the polyurethanes withsignificant areas of hydrophobic segment which can be effective indispersing pigments. While not being bound by theory, these areas ofhydrophobic segment may be effective as the part of the dispersant thatis associated with the pigment surfaces. The polyurethane dispersantmust have at least one Z¹, at least one Z² and at least one Z³ tosatisfy the requirements that the polyurethane contains an aqueousdispersing moiety, and cross-linkable moieties both pendent to thepolymer backbone and terminal to the polymer chain. The blending of Z¹,Z² and Z³ in the polyurethane can be in any sequence. In certaincircumstances, Z² can be the same as Z¹ , and in some othercircumstances, Z² can be the same as Z³, as long as there arecross-linkable moieties, as defined above, on Z². Depending on thesequence of addition during the synthesis of the polyurethane, the R²component (combination of Z¹, Z² and Z³) can be random or in blocks.

Difunctional Isocyanate Reactant (Z²) and Polyol (Z³)

Often Z² and Z³ are derived from polyolefins that are available fromShell as KRATON LIQUID L and Mitsubishi Chemical as POLYTAIL H. Morespecifically, Z² and Z³ can be derived from polyester diols,polycarbonate diols, polyestercarbonate diols and polyacrylate diols.

Suitable polyester polyols include reaction products of polyhydric;dihydric alcohols to which trihydric alcohols may optionally be added,and polybasic (typically dibasic) carboxylic acids. Trihydric alcoholsare limited to at most about 2 weight % such that some branching canoccur but no significant cross-linking would occur, and may be used incases in which modest branching of the NCO prepolymer or polyurethane isdesired. Instead of these polycarboxylic acids, the correspondingcarboxylic acid anhydrides, or polycarboxylic acid esters of loweralcohols, or mixtures thereof may be used for preparing the polyesters.

The polycarboxylic acids may be aliphatic, cycloaliphatic, aromatic orheterocyclic or mixtures thereof and they may be substituted, forexample, by halogen atoms, or unsaturated. The following are mentionedas examples: succinic acid, adipic acid, suberic acid, azelaic acid,sebacic acid, 1,12-dodecyldioic acid, phthalic acid, isophthalic acid,trimellitic acid, phthalic acid anhydride, tetrahydrophthalic acidanhydride, hexahydrophthalic acid anhydride, tetrachlorophthalic acidanhydride, endomethylene tetrahydrophthalic acid anhydride, glutaricacid anhydride, maleic acid, maleic acid anhydride, fumaric acid,dimeric and trimeric fatty acids such as oleic acid, which may be mixedwith monomeric fatty acids, dimethyl terephthalates and bis-glycolterephthalate.

Typically, polyester diols can be blended with hydroxyl terminatedpoly(butylene adipate), poly(butylene succinate), poly(ethyleneadipate), poly(1,2-propylene adipate), poly(trimethylene adipate),poly(trimethylene succinate), polylactic acid ester diol andpolycaprolactone diol. Other hydroxy terminated polyester diols arecopolyethers comprising repeat units derived from a diol and asulfonated, dicarboxylic acid and prepared, as described in U.S. Pat.No. 6,316,586.

Polycarbonates containing hydroxyl groups include those known, such asthe products obtained from the reaction of diols such aspropanediol-(1,3), butanediol-(1,4) or hexanediol-(1,6), diethyleneglycol, triethylene glycol or tetraethylene glycol, and higher polyetherdiols with phosgene, diarylcarbonates such as diphenylcarbonate,dialkylcarbonates such as diethylcarbonate, or with cyclic carbonatessuch as ethylene or propylene carbonate. Also suitable are polyestercarbonates obtained from the above-mentioned polyesters or polylactoneswith phosgene, diaryl carbonates, dialkyl carbonates or cycliccarbonates.

Polycarbonate diols for blending are optionally selected from the groupconsisting of polyethylene carbonate diol, polytrimethylene carbonatediol, polybutylene carbonate diol and polyhexylene carbonate.

Poly(meth)acrylates containing hydroxyl groups include those common inthe art of addition polymerization such as cationic, anionic and radicalpolymerization and the like. Examples are alpha-omega diols. An exampleof these type of diols are those which are prepared by a “living” or“control” or chain transfer polymerization processes which enables theplacement of one hydroxyl group at or near the termini of the polymer.For further examples of making these diols, see: U.S. Pat. Nos.6,248,839 and 5,990,245.

The MW for the polyols described above is typically less than 5000.Typically the MW for Z³ (a polyol) is less than 3000.

Difunctional Isocyanate Reactant (Z¹)

The difunctional isocyanate reactant Z¹ in Formula I contains an aqueousdispersing moiety that is ionic or ionizable. In the context of thisdisclosure, the term “isocyanate reactant”, or “isocynate reactive”, istaken to include groups well known to those of ordinary skill in therelevant art to react with isocyanates, and typically include hydroxyl,primary amino and secondary amino groups. The term “difunctional” meanscontaining two of the isocyanate reactive groups.

Examples of ionic dispersing groups include carboxylate groups (—COOM),phosphate groups (—OPO₃M₂), phosphonate groups (—PO₃M₂), sulfonategroups (-SO3M), and. quaternary ammonium groups (—NR₃Q), wherein M is acation such as a monovalent metal ion (e.g., Na⁺, K⁺, Li⁺, etc.), H orNR₄ ⁺; Q is a monovalent anion such as chloride or hydroxide; and each Rcan independently be an alkyl, aralkyl, aryl or hydrogen. These ionicdispersing groups are typically located, pendent to the polyurethanebackbone.

The ionizable groups in general correspond to the ionic groups, exceptthat they are in the acid (such as carboxyl —COOH) or base (such asprimary, secondary or tertiary amine —NH₂, —NRH, or —NR₂) form. Theionizable groups are such that they are readily converted to their ionicform during the dispersion/polymer preparation process as discussedbelow.

With respect to compounds which contain isocyanate reactive groups and.ionic or potentially ionic groups, the isocyanate reactive groups aretypically amino and hydroxyl groups. The potentially ionic groups ortheir corresponding ionic groups may be cationic or anionic, althoughthe anionic groups are preferred. Specific examples of anionic groupsinclude carboxylate and sulfonate groups. Examples of cationic groupsinclude quaternary ammonium groups and sulfonium groups.

In the case of anionic group substitution, the groups can be carboxylicacid groups, carboxylate groups, sulphonic acid groups, sulphonategroups, phosphoric acid groups and phosphonate groups. The acid saltsare formed by neutralizing the corresponding acid groups either priorto, during or after formation of the NCO prepolymer.

Suitable compounds for incorporating carboxyl groups are described inU.S. Pat. Nos. 3,479,310, 4,108,814 and 4,408,008. Examples ofcarboxylic group-containing compounds are the hydroxy-carboxylic acidscorresponding to the formula (HO)_(p)Q(COOH)_(q), wherein Q is C₁-C₁₀alkyl, p is 1 or 2, and q is 1 to 3. Examples of thesehydroxy-carboxylic acids include citric acid, tartaric acid, andhydroxypivalic acid. Optional dihydroxy alkanoic acids include theα,α-dimethylol alkanoic acids represented by the structure of Formula IIbelow:

wherein Q′ is hydrogen or C₁-C₈ alkyl. Additional α,α-dimethylolalkanoic acids are represented by the structural formulaR⁵C—(CH₂OH)₂—COOH, wherein R⁵ is hydrogen or C₁-C₈ alkyl. Examples ofthese ionizable diols include, but are not limited to, dimethylolaceticacid, 2,2′-dimethylolbutanoic acid, 2,2′-dimethylolpropionic acid(DMPA), and 2,2′-dimethylolbutyric acid. Suitable carboxylates alsoinclude H₂N—(CH₂)₄—CH(CO₂H)—NH₂, and H₂N—CH₂—CH₂—NH—CH₂—CH₂—CO₂Na.

Typical sulfonate groups for incorporation into the polyurethanesinclude diol sulfonates described in U.S. Pat. No. 4,108,814. Suitablediol sulfonate compounds also include hydroxyl terminated copolyetherscomprising repeat units derived from the reaction of a diol and asulfonated dicarboxylic acid. Specifically, the sulfonated dicarboxylicacid is 5-sulfo-isophthalic acid and the diol is 1,3-propanediol. Othersuitable sulfonates include the ones represented by formulaH₂N—CH₂—CH₂—NH—(CH₂)_(r)—SO₃Na, wherein r is 2 or 3.

When the ionic stabilizing groups are acids, the acid groups areincorporated in an amount sufficient to provide an acid group contentfor the polyurethane, known by those skilled in the art as acid number(mg KOH per gram solid polymer), of at least 6, typically at least 10,and even more typically 20 milligrams KOH per 1.0 gram of polyurethane.The upper limit for the acid number (AN) is about 120, and typicallyabout 100.

Within the context of this disclosure, the term “neutralizing agents” ismeant to embrace all types of agents which are useful for convertingpotentially ionic or ionizable groups to ionic groups. When amines areused as the neutralizing agent, the chain terminating reaction producingthe urea termination is typically completed prior to the addition of theneutralizing agent that can also act as an isocyanate reactive group.

In order to convert an anionic group to its salt form before, during orafter its incorporation into a prepolymer, either volatile ornonvolatile basic materials may be used to form the counterion of theanionic group. Volatile bases are those wherein at least about 90% ofthe base used, to form the counterion of the anionic group volatilizesunder the conditions used to remove water from the aqueous polyurethanedispersions. Nonvolatile bases are those wherein at least about 90% ofthe base does not volatilize under the conditions used to remove waterfrom the aqueous polyurethane dispersions.

Suitable volatile basic organic compounds for neutralizing the potentialanionic groups are the primary, secondary or tertiary amines. Examplesof these amines are trimethyl amine, triethyl amine, triisopropyl amine,tributyl amine, N,N-dimethyl-cyclohexyl amine, N,N-dimethylstearylamine, N,N-dimethylaniline, N-methylmorpholine, N-ethylmorpholine,N-methylpiperazine, N-methylpyrrolidine, N-methylpiperidine,N,N-dimethyl-ethanol amine, N,N-diethyl-ethanol amine, triethanolamine,N-methyldiethanol amine, dimethylaminopropanol, 2-methoxyethyldimethylamine, N-hydroxyethylpiperazine, 2-(2-dimethylaminoethoxy)-ethanol and5-diethylamino-2-pentanone.

Suitable nonvolatile bases include alkoxides, hydroxides, carbonates orbicarbonates of monovalent metals, especially the alkali metals,lithium, sodium and potassium.

When the anionic groups on the polyurethane are neutralized, theyprovide hydrophilicity to the polymer and better enable it to stablydisperse pigment in water. However, if may be desirable to control thedegree of neutralization. When the anionic groups on the polyurethaneare partially neutralized, the polyurethane becomes more hydrophobic andtherefore adsorbs onto the pigment surface. Reducing the amount of theun-adsorbed polymer from the pigment dispersion provides an advantageouscondition for the cross-linkable moieties on the polyurethane, adsorbingonto the pigment surface, to react with a cross-linking agent withoutthe competition from cross-linkable moieties on the un-adsorbedpolyurethane. Typically the degree of neutralization is from 40% to100%, and more typically from 50% to 70%, depending on the acid numberof the polyurethane.

Capping of the Polyurethane

The capping agent for terminating the polyurethane chain is usually aprimary or secondary amine, an alcohol, or a mecapto. In Formula I, thecapping agent is shown as a X—R³—Y-substituent on the polyurethane.

The amount of capping agent employed should be approximately equivalentto the free isocyanate groups in the prepolymer. The ratio of activehydrogens from amine in the capping agent to isocyanate groups in theprepolymer is in the range of from about 1.0:1.0to about 3.0:1.0, moretypically from about 1.0:1.0 to about 1.5:1.0, and still more typicallyfrom about 1.0:1.0 to about 1.05:1, on an equivalent basis. Although anyisocyanate groups that are not terminated with an amine can react withother isocyanate reactive functional group or water, the ratios ofcapping agent to isocyanate group is chosen to ensure a ureatermination. Amine termination of the polyurethane is avoided by thechoice and amount of capping agent leading to a urea terminatedpolyurethane. This results in better molecular weight control and betterproperties when used as a particle dispersant, and ease in handling whenadded to formulations.

Any primary or secondary amines substituted with reactive isocyanategroups may be used as chain terminators. Especially useful are aliphaticprimary or secondary monoamines, or diamines. Less reactive isocyanategroups such as hydroxyl, carboxyl, and mercapto could also be used.Example of amines useful as chain terminators include, but are notrestricted to, diethanolamine, monoethanolamine, 3-amino-1-propanol,isopropanolamine, N-ethylethanolamine, diisopropanolamine,6-aminocaproic acid, 8-aminocaprylic acid, and 3-aminoadipic acid. Antypical isocyanate reactive chain terminator is diethanolamine. Thehydroxyl functionalities on diethanolamine serve as cross-linkingmoieties terminal to the polyurethane chain.

Polyisocyanate Component

Suitable polyisocyanates are those that contain either aromatic,cycloaliphatic or aliphatic groups bound to the isocyanate groups.Mixtures of these compounds may also be used. If aromatic isocyanatesare used, cycloaliphatic or aliphatic isocyanates can be present aswell.

Any diisocyanate useful in preparing polyurethanes via its reaction withpolyether glycols, diols or amines can be used in this invention.

Examples of suitable di isocyanates include, but are not limited to,2,4-toluene diisocyanate (TDI), 2,6-toluene diisocyanate, trimethylhexamethylene diisocyanate (TMDI), 4,4′-diphenylmethane diisocyanate(MDI), 4,4′-dicyclohexylmethane diisocyanate (H₁₂MDI),3,3′-dimethyl-4,4′-biphenyl diisocyanate (TODI), dodecane diisocyanate(C₁₂DI), m-tetramethylene xylylene diisocyanate (TMXDI), 1,4-benzenediisocyanate, trans-cyclohexane-1,4-diisocyanate, 1,5-naphthalenediisocyanate (NDI), 1,6-hexamethylene diisocyanate (HDI), 4,6-xylyenediisocyanate, isophorone diisocyanate (IPDI), and combinations thereof.

Small amounts, typically less than about 3% by weight based on theweight of the diisocyanate, of monoisocyanates or polyisocyanates can beused, in a mixture with the diisocyanate. Examples of usefulmonoisocyanates include alkyl isocyanates such as octadecyl isocyanateand aryl isocyanates such as phenyl isocyanate. Examples of usefulpolyisocyanates are triisocyanatotoluene HDI trimer and polymeric MDI.

Cross-linking of Dispersant

The polyurethane dispersants have cross-linkable functional moietiesboth pendent to the polymer backbone and terminal to the polymer chain.The dispersants are thus capable of reacting with a cross-linkingcompound. Identified in the table below are suitable cross-linkablefunctional groups that are in the polymeric dispersant and the companioncross-linking groups that may be present in the cross-linking compound.

Cross-linkable Moieties Cross-linking Groups COOH Epoxide, Carbodiimide,Oxazoline, N-Methyol Hydroxyl Epoxide, Silane, Isocyanate, N-MethyolAmino Epoxide, Carbodiimide, Oxazoline, N-Methyol

The cross-linkable moieties can be situated at the terminals of thepolymer chain (group X in Formula I) or be incorporated into the R²group (in Formula I) of the polyurethane dispersant by selection ofappropriate Z². Mixtures of these cross-linkable moieties may also bepresent in the polyurethane dispersant. Useful cross-linking compoundsare those which are soluble or insoluble in the aqueous vehicle,including m-tetramethylxylene diisocyanate (TMXDI), isophoronediisocyanate (IPDI), trimethylopropane polyglycidyl ether, polyglycerolpolyglycidyl ether, oxazoline-functional polymers, waterbornepolycarbodiimide resin, and silane.

The mole ratio of the cross-linkable moiety on the polymer chain to thecross-linking groups on the cross-linking agent is from 15:1 to 1:1.5.typically from 9:1 to 1:1.1, and most typically from 8:1 to 1:1. Incalculating the mole ratio, all cross-linkable moieties on the polymerchain and all cross-linking groups on the cross-linking agent areincluded

Colorants

A wide variety of organic and inorganic pigments, alone or incombination, may be dispersed with the polyurethane dispersant toprepare an ink, especially an ink-jet ink. The term “pigment” as usedherein means an insoluble colorant that requires to be dispersed with adispersant and processed under dispersive conditions in the presence ofa dispersant. The colorant also includes dispersed dyes. The dispersionprocess results in a stable dispersed pigment. The pigment used with theinventive polyurethane dispersants does not include self-dispersedpigments. The pigment particles are sufficiently small to permit freeflow of the ink through the ink-jet printing device, especially at theejecting nozzles that usually have a diameter ranging from about 10micron to about 50 micron. The particle size also has an influence onthe pigment dispersion stability, which is critical throughout the lifeof the ink. Brownian motion of minute particles will help prevent theparticles from flocculation. It is also desirable to use small particlesfor maximum color strength and gloss. The range of useful particle sizeis typically about 0.005 micron to about 15 micron. Typically, thepigment particle size should range from about 0.005 to about 5 micronand, most typically, from about 0.005 to about 1 micron. The averageparticle size as measured by dynamic light scattering is less than about500 nm, typically less than about 300 nm.

The selected pigment(s) may be used in dry or wet form. For example,pigments are usually manufactured in aqueous media, and the resultingpigments are obtained, as a water-wet presscake. In presscake form, thepigment does not agglomerate to the extent like it is in dry form. Thus,pigments in water-wet presscake form do not require as much mixingenergy to de-agglomerate in the premix process as pigments in dry form.Representative commercial dry pigments are listed in U.S. Pat. No.5,085,698.

Some examples of pigments with coloristic properties useful in inkjetinks include: cyan pigments from Pigment Blue 15:3 and Pigment Blue15:4; magenta pigments from Pigment Red 122 and Pigment Red 202; yellowpigments from Pigment Yellow 14, Pigment Yellow 95, Pigment Yellow 110,Pigment Yellow 114, Pigment Yellow 128 and Pigment Yellow 155; redpigments from Pigment Orange 5, Pigment Orange 34, Pigment Orange 43,Pigment Orange 62, Pigment Red 17, Pigment Red 49:2, Pigment Red 112,Pigment Red 149, Pigment Red 177, Pigment Red 178, Pigment Red 188,Pigment Red 255and Pigment Red 264; green pigments from Pigment Green 1,Pigment Green 2, Pigment Green 7 and Pigment Green 36; blue pigmentsfrom Pigment Blue 60, Pigment Violet 3, Pigment Violet 19, PigmentViolet 23, Pigment Violet 32, Pigment Violet 36 and Pigment Violet 38;white pigments such as TiO₂ and ZnO; and black pigment carbon black. Thepigment names and abbreviations used herein are the “C.I.” designationfor pigments established by Society of Dyers and Colourists, Bradford,Yorkshire, UK and published in The Color Index, Third Edition, 1971.

In the case of organic pigments, the ink may contain up to approximately30%, typically from 0.1% to about 25%, and more specifically from 0.25%to 10% of pigment, by weight based on the total ink weight. If aninorganic pigment is selected, the ink will tend to contain higherpercentages by weight of pigment than with comparable inks employingorganic pigment, since inorganic pigments generally have higherdensities than organic pigments.

The polyurethane polymer dispersant is typically present in the range offrom 0.1% to 20%, and more specifically from 0.2% to about 10%, byweight based on the weight of the total ink composition.

Binder

A binder is a polymeric compound or a mixture of polymeric compoundsthat is added to the ink formulation. The binder can impart propertiesto the final printed material that, for example, gives greaterdurability to the printed material Typical polymers used as binders ininkjet inks include polyurethane dispersions and polyurethane solutions,acrylics, styrene acrylics, styrene butadienes, styrene butadieneacrylonitriles, neoprenes, ethylene acrylic acids, ethylene vinylacetate emulsions, latexes and the like. The binder may be a solution orstabilized as an emulsion by having ionic substituents such ascarboxylic acids, sulfur containing acids, amine groups, and othersimilar ionic groups. Co-stabilizers that are non-ionic in nature, suchas those containing polyethyleneoxide, may also be present.Alternatively, the binder may be stabilized by external surfactants.

The binder can be used singly or in combination with other binders.Typically, the binder is a polyurethane.

The binder is typically present in an ink in an amount of at least 0.2%by weight based on the total weight of the ink.

Preparation of Polyurethane Dispersant

The polyurethane dispersants of the present invention can be prepared bya one-step mixing or a stepwise method. The physical form of thepolyurethane prior to its use as a dispersant is an aqueous dispersion.In the one-step mixing process, isocyanate terminated polyurethane isprepared by mixing Z¹, Z² and Z³ in a solvent, followed by adding adiisocyanate to the mixture. This reaction is conducted at from about40° C. to about 100° C., and typically from about 50° C. to about 90° C.The ratio of isocyanate to isocyanate reactive groups (Z¹, Z² and Z³) isfrom about 1.3:1 to about 1.05:1, and more typically from about 1.25:1to about 1.1:1. When the targeted percentage of isocyanate content isreached, a primary or secondary amine capping agent is added. Thepolyurethane solution is then converted to an aqueous dispersion via theaddition of de-ionized water under a high shearing operation. Volatilesolvent(s), if present, are distilled under reduced pressure.

The NCO-functional prepolymers should be substantially linear, and thismay be achieved by maintaining the average functionality of theprepolymer starting components at or below 2:1.

In the stepwise method, a polyurethane is prepared by dissolving the Z¹reactant in a solvent, followed by adding a diisocyanate to the mixture.Once the initial percentage of isocyanate content target is reached, theZ² and Z³ components are added. This reaction is conducted at from about40° C. to about 100° C., and typically from about 50° C. to about 90° C.The typical ratio of isocyanate to isocyanate reactive groups is fromabout 1.3:1 to about 1.05:1, and more typically from about 1.25:1 toabout 1.1:1. Alternately, the Z² and Z³ reactants may be reacted in thefirst step, and the Z¹ reactant may be added after the initialpercentage of isocyanate content target is reached. When the finaltargeted percentage of isocyanate content is reached, a capping agent isadded. The polyurethane solution is then converted to an aqueouspolyurethane dispersion via the addition of water under a high shearingoperation. Volatile solvent(s), if present, are distilled under reducedpressure.

Catalysts are not necessary for the preparation of the polyurethanes,but may provide advantages in a large scale manufacturing process. Thecatalysts most widely used are tertiary amines and organo-tin compoundssuch as stannous octoate, dibutyltin dioctoate and dibutyltin dilaurate.

Preparation of the polyurethane for subsequent conversion to adispersion is facilitated by using a solvent. Suitable solvents arethose that are miscible with water and inert to isocyanates and otherreactants utilized in forming the polyurethanes. If it is desired toprepare a solvent-free dispersion, the solvent used should havesufficient volatility to allow its removal by distillation. Typicalsolvents useful in the practice of the present invention are acetone,methyl ethyl ketone, toluene, and N-methyl pyrolidone. Alternatively,the polyurethane can be prepared in a melt with less than 5% of solvent.

Mixtures of compounds or polymers having mixed NCO reactive groups canalso be used in the preparation of the polyurethane of the presentinvention.

Processing conditions for preparing the NCO containing prepolymers arewell known to one skilled in the art. The finished NCO-containingprepolymer should have an isocyanate content of from about 1 to about20%, typically from about 1 to about 10% by weight, based on the weightof prepolymer solids.

As described above, a sufficient amount of the ionic groups must beneutralized so that the resulting polyurethane can have a proper balanceof hydrophilicity and hydrophobicity. Typically the degree ofneutralization is from 40% to 100%, and more typically from 50% to 70%,depending on the acid number of the polyurethane.

Suitable neutralizing agents for converting the acid groups to saltgroups include tertiary amines, alkali metal cations and ammonia.Neutralizing agents can be trialkyl-substituted tertiary amines, such astriethyl amine, tripropyl amine, dimethylcyclohexyl amine,dimethylethanol amine, and triethanol amine and dimethylethyl amine.Substituted amines such as diethyl ethanol amine or diethanol methylamine are also useful neutralizing agents.

Neutralization may take place at any point in the process. Typicalprocedures include at least some neutralization of the prepolymer, whichis then chain extended/terminated in water in the presence of additionalneutralizing agent.

The capping agent for terminating the polyurethane chain is usually aprimary or secondary amine, an alcohol, or a mecapto. The amount ofcapping agent employed should be approximately equivalent to the freeisocyanate groups in the prepolymer. The ratio of active hydrogens fromamine in the capping agent to isocyanate groups in the prepolymer is inthe range of from about 1.0:1.0 to about 3.0:1.0, more typically fromabout 1.0:1.0 to about 1.5:1.0, and still more typically from about1.0:1.0 to about 1.05:1, on an equivalent basis.

Conversion of the polyurethane obtained from the methods described aboveto an aqueous dispersion is completed by addition of de-ionized water.If desired, solvent can then be removed partially or substantially bydistillation under reduced pressure. The final product is a stable,aqueous polyurethane dispersion having a solids content of up to about60% by weight, typically from about 10% to about 60% by weight, and moretypically from about 20% to about 45% by weight. However, it is alwayspossible to dilute the dispersions to any minimum solids contentdesired. The solids content of the resulting dispersion may bedetermined by drying the sample in an oven at 150° C. for 2 hours andcomparing the weights before and after drying. The particle size isgenerally below about 1.0 micron, and typically between about 0.01 toabout 0.5 micron. The average particle size should be less than about0.5 micron, and typically between about 0.01 to about 0.3micron. Thesmall particle size enhances the stability of the dispersed particles

Preparation of Pigmented Dispersions

The pigmented dispersions used in this invention can be prepared usingany conventional milling process known in the art. Most millingprocesses use a two-step process involving a first mixing step followedby a second grinding step. The first step comprises mixing of all theingredients, that is, pigment, dispersants, liquid carriers,neutralizing agent and any optional additives to provide a blended“premix”. Typically ail liquid ingredients are added first, followed bythe dispersants, and lastly the pigment. Mixing is generally done in astirred mixing vessel, and a high-speed disperser (HSD) is particularlysuitable for the mixing step. A Cowels type blade attached, to the HSDand operated at from 500 rpm to 4000 rpm, and more typically from 2000rpm to 3500 rpm, provides optimal shear to achieve the desired mixing.Adequate mixing is usually achieved after mixing under the conditionsdescribed above for a period of from 15 to 120 minutes.

The second step comprises grinding of the premix to produce a pigmenteddispersion. Typically, grinding involves a media milling process,although other milling techniques can also be used. In the presentinvention, a lab-scale Eiger Minimill (Model M250, VSE EXP) manufacturedby Eiger Machinery Inc., Chicago, Ill. is employed. Grinding wasaccomplished by charging about 820 grams of 0.5 YTZ® zirconia media tothe mill. The mill disk is operated, at a speed between 2000 rpm and4000 rpm, and typically between 3000 rpm and 3500 rpm. The dispersion isprocessed using a re-circulation grinding process with a typical flowrate through the mill at between 200 to 500 grams/minute, and moretypically at 300 grams/minute. The milling may be done using a stagedprocedure in which a fraction of the solvent is held out of the grindand added, after milling is completed. This is done to achieve optimalrheology that maximizes grinding efficiency. The amount of solvent heldout during milling varies by dispersion, and is typically between 200 to400 grams for a batch size with a total of 800 grams. Typically, thedispersions of the present invention are subjected to a total of 4 hoursof milling.

For black dispersions, an alternate milling process using aMicrofluidizer can be used. Microfluidization is a non-media millingprocess in which milling is done by pigment impingement through nozzlesunder high pressures. Typically, pigment dispersions are processed at15,000 psi with a flow rate of 400 grams/minute for a total of 12 passesthrough the mill. In making the black dispersions in the Examples, alab-scale (Model M-110Y, available from Microfluidics of Newton, Mass.)high pressure pneumatic Microfluidizer with a diamond Z Chamber wasemployed.

Fillers, plasticizers, pigments, carbon black, silica sols, otherpolymer dispersions and the known leveling agents, wetting agents,antifoaming agents, stabilizers, and other additives known for thedesired end use, may also be incorporated into the dispersions.

Preparation of Cross-linked Pigment Dispersion

In the cross-linking step, a cross-linking compound is mixed with thepigmented dispersions prepared above at room temperature or elevatedtemperature for a period from 6 h to 8 h. To facilitate thecross-linking reaction, it may be desirable to add a catalyst. Usefulcatalysts can be those that are either soluble or insoluble in theliquid and can be selected depending upon the crosslinking reactions.Some suitable catalysts include dibutyltin dilaurate (DBTDL), tributylamine (“TBA”) and dimethyldodecyl amine. After the cross-linkingreaction is completed, the pH of the cross-linked dispersion can beadjusted to at least about 8.0, more typically to between 8.0 and 12.0,and most typically between 8.0 and 11.0, if needed. Optionally, thedispersion may be further processed using conventional filtrationprocedures known in the art. The dispersions may be processed usingultrafiltration techniques that remove co-solvents and othercontaminants, ions or impurities from the dispersion. Each dispersioncan be then tested for pH, conductivity, viscosity and particle size.Dispersion stability is deemed important to demonstrating the utility ofthe dispersant employed.

Fillers, plasticizers, pigments, carbon black, silica sols, otherpolymer dispersions and the known leveling agents, wetting agents,antifoaming agents, stabilizers, and other additives known for thedesired end use, may also be incorporated into the dispersions.

Ink Vehicle

The pigmented ink of this disclosure comprises an ink vehicle typicallyan aqueous ink vehicle, also known as an aqueous carrier medium, theaqueous dispersion and optionally other ingredients.

The ink vehicle is the liquid carrier (or medium) for the aqueousdispersion(s) and optional additives. The term “aqueous ink vehicle”refers to an ink vehicle comprised of water or a mixture of water andone or more organic, water-soluble vehicle components commonly referredto as co-solvents or humectants. Selection of a suitable mixture dependson requirements of the specific application, such as desired surfacetension and viscosity, the selected pigment, drying time of thepigmented ink jet ink, and the type of paper onto which the ink will beprinted. Sometimes in the art, when a co-solvent can assist in thepenetration and drying of an ink on a printed substrate, it is referredto as a penetrant.

Examples of water-soluble organic solvents and humectants include:alcohols, ketones, keto-alcohols, ethers and others, such asthiodiglycol, Sulfolane, 2-pyrrolidone, 1,3-dimethyl-2-imidazolidinoneand caprolactam; glycols such as ethylene glycol, diethylene glycol,triethylene glycol, tetraethylene glycol, propylene glycol, dipropyleneglycol, tripropylene glycol, trimethylene glycol, butylene glycol andhexylene glycol; addition polymers of oxyethylene or oxypropylene suchas polyethylene glycol, polypropylene glycol and the like; triols suchas glycerol and 1,2,6-hexanetriol; lower alkyl ethers of polyhydricalcohols, such as ethylene glycol monomethyl ether, ethylene glycolmonoethyl ether, diethylene glycol monomethyl, diethylene glycolmonoethyl ether; lower dialkyl ethers of polyhydric alcohols, such asdiethylene glycol dimethyl or diethyl ether; urea and substituted ureas.

A mixture of water and a polyhydric alcohol, such as diethylene glycol,is typical as the aqueous ink vehicle. In the case of a mixture of waterand diethylene glycol, the ink vehicle usually contains from 30% waterand 70% diethylene glycol to 95% water and 5% diethylene glycol, moretypically from 60% water and 40% diethylene glycol to 95% water and 5 %diethylene glycol. Percentages are based on the total weight of the inkvehicle. A mixture of water and butyl carbitol is also an effective inkvehicle.

The amount of ink vehicle in the ink is typically in the range of from70% to 99.8%, and more typically from 80% to 99.8%, by weight based ontotal weight of the ink.

The ink vehicle can be made to be fast penetrating (rapid drying) byincluding surfactants or penetrating agents such as glycol ethers and1,2-alkanediols. Glycol ethers include ethylene glycol monobutyl ether,diethylene glycol mono-n-propyl ether, ethylene glycol mono-iso-propylether, diethylene glycol mono-iso-propyl ether, ethylene glycolmono-n-butyl ether, ethylene glycol mono-t-butyl ether, diethyleneglycol mono-n-butyl ether, tri ethylene glycol mono-n-butyl ether,diethylene glycol mono-t-butyl ether, 1-methyl-1-methoxybutanol,propylene glycol mono-t-butyl ether, propylene glycol mono-n-propylether, propylene glycol mono-iso-propyl ether, propylene glycolmono-n-butyl ether, dipropylene glycol mono-n-butyl ether, dipropyleneglycol mono-n- propyl ether, and. dipropylene glycol mono-isopropylether. Typical 1,2-alkanediols are C₄-C₆ alkanediols with 1,2-hexanediolbeing most typical. Suitable surfactants include ethoxylated acetylenediols (e.g. Surfynol® series commercially available from Air Products),ethoxylated alkyl primary alcohols (e.g. Neodol® series commerciallyavailable from Shell) and secondary alcohols (e.g. Tergitol® seriescommercially available from Union Carbide), sulfosuccinates (e.g.Aerosol® series commercially available from Cytec), organosilicones(e.g. Silwet® series commercially available from Witco) and fluorosurfactants (e.g. Zonyl® series commercially available from DuPont).

The amount of glycol ether(s) and 1,2-alkanediol(s) added is typicallyin the range of from 1% to 15%, and more typically from 2% to 10% byweight, based on the total weight of the ink. Surfactants may be used,typically in the amount of from 0.01% to 5% and more typically from 0.2%to 2%, by weight based on the total weight of the ink.

Biocides may be used to inhibit growth of microorganisms.

Pigmented Inkjet inks typically have a surface tension in the range ofabout 20 mN.m⁻¹ to about 70 mN.m⁻¹, at 25° C. Viscosity can be as highas 30 mPa·s at 25° C., but is typically somewhat lower. The ink hasphysical properties compatible with a wide range of ejecting conditions,materials construction and the shape and size of the nozzle. The inksshould have excellent storage stability for long periods so as not toclog to a significant extent in an ink jet apparatus. Further, the inkshould not corrode parts of the Inkjet printing device it comes incontact with, and it should be essentially odorless and non-toxic.

Although not restricted to any particular viscosity range or printhead,the inks of the disclosure are particularly suited to lower viscosityapplications. Thus the viscosity (at 25° C.) of the inks of thisdisclosure may be less than about 7 mPa·s, or less than about 5 mPa·s,and even more advantageously, less than about 3.5 mPa·s

The following examples illustrate the invention without, however, beinglimited thereto.

EXAMPLES Extent of Polyurethane Reaction

The extent of polyurethane reaction was determined by a titration withdibutylamine to detect the isocyanate content (NCO %), a common methodused in urethane chemistry.

In this method, a sample of the isocyanate containing prepolymer isreacted with a known amount of dibutylamine solution, and the residualamine is back titrated with aqueous HCl.

Particle Size Measurements

The particle size for the polyurethane dispersions, pigments and theinks were determined by dynamic light scattering using a Microtrac® UPA150 analyzer from Honeywell/Microtrac (Montgomeryville Pa.).

This technique is based on the relationship between the velocitydistribution of the particles and the particle size. Laser generatedlight is scattered from each particle and is Doppler shifted by theparticle Brownian motion. The frequency difference between the shifted,light and the unshifted light is amplified, digitalized and analyzed toderive the particle size distribution. Results are reported as D50 andD95.

Solid Content Measurement

Solid content for the solvent free polyurethane dispersions was measuredwith a moisture analyzer, Model MA50 from Sartorius. For polyurethanedispersions containing a high boiling solvent, such as NMP,tetraethylene glycol dimethyl ether, or sulfolane, the solid content wasdetermined by the weight difference before and after baking in an ovenset at 150° C. oven for 180 minutes.

Polyurethane Dispersant 1 (PEA Terminated TMXDI/UH-50/DMPA)

To a dry, alkali- and acid-free, 2 liter flask equipped with anadditional funnel, a condenser and a stirrer, under a nitrogenatmosphere was added Eternacoll® UH-50 (117.0 g), dimethylol propionicacid (87.0 g) and Sulfolane (220.0 g). The contents were heated to 115°C. and mixed under a nitrogen gas purge for 30 minutes. The temperaturewas then lowered to 60° C. and DBTDL (0.08 g) was added followed byTMXDI (238.0 g) via the addition funnel. The residual TMXDI in theadditional funnel was rinsed into the flask with Sulfolane (15.0 g). Thestirred reaction mass was allowed to exotherm. When exotherm began toslow, the temperature was maintained at 100° C. while monitoring theisocyanate content until it reached 1.06%. The temperature was loweredto 60° C. To the flask was added DEA (18.04 g) via the additional funnelfollowed by rinsing the residual BMEA in additional funnel into theflask with. Sulfolane (5.0 g). The mixture was maintained at 60° C. for90 minutes. A solution of 45% KOH in water (56.56 g) and additionalde-ionized, water (776.87 g) were added over a period of 5 minutes togive a 70% neutralized polyurethane resin in water. This was allowed tostir and cool to room temperature to provide a polyurethane dispersionwith 27.49% of solids and. a measured, acid number of 79.03 mg KOH/grampolymer.

Polyurethane Binder 1 (BMEA Terminated IPDI/T650/DMPA)

To a dry, alkali- and acid-free, 2 liter flask equipped with anadditional funnel, a condenser and a stirrer, under a nitrogenatmosphere were added Terathane® 650 (291.5 g), dimethylol propionicacid (61.85 g), tetraglyme (482.59 g) and DBTDL (0.04 g). The contentswere heated to 40° C. and mixed under a nitrogen gas purge for 30minutes. IPDI (222.86 g) was added via the addition funnel over 60minutes. The residual IPDI in. the additional funnel was rinsed into theflask with tetraglyme (9.6 g). The stirred reaction mass was allowed toexotherm to 50° C., but not to exceed 53° C., while monitoring theisocyanate content until it reached 0.84%. To the flask was added BMEA(20.94 g) via the additional funnel. The mixture was maintained, at 50 C. for 90 minutes. A solution of 45% KOH in water (57.5 g) andadditional de-ionized water (1372.4 g) were added over a period of 5minutes to give a dispersed polyurethane resin in water. This wasallowed to stir and cool to room temperature to provide a polyurethanedispersion with 24.17% of solids and a measured acid number of 45.0 mgKOH/gram polymer.

Preparation of Pigmented Dispersion K1

The following procedure was used to prepare a black pigmented dispersionusing Nipex 180 and Dispersant 1. Using an microfluidizer, a premix wasprepared at typically 20-30% pigment loading and the targeted dispersantlevel was selected at a pigment/dispersant (P/D) ratio of 2.0. A P/D of2.0 corresponds to a 40% dispersant level on pigment. A co-dispersant,Surfynol 104 in Dowanol DPM at a P/D=100 was added to the totaldispersion formulation to facilitate wetting of pigment and dissolutionof dispersant in the premix stage for ease of grinding during millingstage. Dispersant 1 was pre-neutralized with KOH to facilitatesolubility and dissolution into water. An additional 6.91 g of a 45% KOHsolution in water was added. During the premix stage and milling stage,de-ionized water (1200 g) was added to adjust viscosity and controltemperature. After completion of the milling stage, the remainingletdown of de-ionized water (450.0 g) was added and thoroughly mixed.The final pigment dispersion contains 23.15% of solids.

The pigment dispersion was purified using an ultrafiltration process toremove co-solvent(s) and excess dispersant, and filter out otherimpurities that may be present. After completion, the pigment level inthe dispersion was reduced to about 10 to 15%. A single blackdispersion, listed in Table 1 was prepared using the PolyurethaneDispersant 1.

TABLE 1 Pigmented Pigment/ Polyurethane Particle Size Dispersion PigmentDispersant Dispersant No. D50 (nm) D95 (nm) K1 Nipex 180 2 1 107 185

Preparation of Cross-linked Pigment Dispersion XL-K1

In the cross-linking step, Denacol® 321 was mixed with one of thepigmented Dispersion K1, and heated at temperatures between 60° C. and80° C. with efficient stirring for 6-8 hours. After the cross-linkingreaction was completed, the pH was adjusted to at least about 8.0 ifneeded. The composition of the cross-linked Pigment Dispersion XL-K1issummarized in Table 2.

TABLE 2 Cross-linked Pigmented Cross-linkable Cross-linking DispersionDispersion Moiety Compound XL-K1 K1 COOH, OH Denacol ® 321

Preparation of Ink and Testing of Stability

The inks were prepared by conventional processes known to one skilled inthe art using the cross-linked Dispersion XL-K1 and PolyurethaneBinder 1. A comparative ink without the presence of Polyurethane Binder1 was also prepared. The inventive ink was processed by routineoperations using a typical ink vehicle suitable for ink-jet inkformulation targeting 3% by weight of the cross-linked. Dispersion XL-K1and 1% by weight of the Polyurethane Binder 1 in the final ink. Thecomparative ink was made the same way, but without any PolyurethaneBinder 1.

As shown in Table 3 below, the ink made with cross-linked blackDispersion 1together with a binder when printed in general showed loweroptical density, better smudge and highlighter smear properties comparedto a comparative ink without the presence of the binder. When printed onXerox 4200, no changes in optical density, smudge and highlighter smearproperties were observed between the ink with the binder and the inkwithout the binder.

TABLE 3 Optical Highlighter Smear^(#) Paper Ink Density Smudge* 10 min 1hr 10 min 1 h HP XL-K1, 1.32 3 4 4 2 2 Bright no binder White XL-K1,1.25 4 4 4 2 3 1% Binder 1 HP XL-K1, 1.34 2 3 3 1 1 Multi- no binderpurpose XL-K1, 1.22 3 4 4 1 2 1% Binder 1 Xerox XL-K1, 0.84 4 5 5 4 44200 no binder XL-K1, 0.84 4 5 5 4 4 1% Binder 1 HP XL-K1, 1.67 3 4 4 33 Bro- no binder chure XL-K1, 1.44 4 5 5 4 4 1% Binder 1 *Visual Ratingfor Smudge 0 - Ink largely removed 2 - Severe smudge 3 - Moderate smudge4 - Very slight smudge 5 - No smudge visible ^(#)Visual Rating forHighlighter Smear 0 - Ink largely removed from stripe with highlighter1 - Severe smear, considerable color transfer, may be some damage tostripe 2 - Noticeable smear, run full width of area between stripes 3 -Moderate smear, may be full width of highlighter, but light in color 4 -Slight smear, narrow, doesn't run clear to next stripe 5 - No smearvisible

1. An ink-jet ink comprising an aqueous ink vehicle, an aqueous pigmentdispersion and a polymeric binder, wherein said aqueous pigmentdispersion comprises a colorant and a polyurethane dispersant, and saidpolymeric binder is non-reactive to said colorant, and wherein saidpolyurethane dispersant is comprised of a polymer with: (a) an aqueousdispersing moiety, and (b) a cross-linkable moiety that is cross-linkedwith a cross-linking agent, wherein said cross-linkable moiety ispendent to the polymer backbone and terminal to the polymer chain;wherein the polyurethane dispersant comprises at least one compound ofthe general structure of Formula I:

wherein each X is independently OH, SH, COOH or NHR₄; each Y isindependently O, S or NR₄; each W is N, O or S; each R¹ is independentlyC₁-C₂₀ alkyl, C₃-C₂₀ substituted alkyl, C₆-C₄₀ aryl or C₉-C₄₀substituted aryl; R² is comprised of difunctional isocyanate reactantsZ¹, Z² and Z³, wherein there is at least one Z¹, at least one Z² and atleast one Z³; each R³ is independently C₁-C₂₀ alkyl or C₃-C₂₀substituted alkyl; each R⁴ is independently —R³—X, H, C₁-C₂₀ alkyl orC₃-C₂₀ substituted alkyl; n is an integer from 2 to 30; Z¹ is adifunctional isocyanate reactant substituted with an aqueous dispersingmoiety; Z² is a difunctional isocyanate reactant substituted with one ormore cross-linkable moieties; and Z³ is a polyol with MW less than 3000.2. The ink of claim 1, wherein the polymeric binder is one or moremembers selected from the group consisting of polyurethane, acrylics,styrene acrylics, styrene butadienes, styrene butadiene acrylonitriles,neoprenes, ethylene acrylic acid copolymer, ethylene vinyl acetate, andmixtures thereof.
 3. The ink of claim 2, wherein the cross-linking agentis one or more members selected from the group consisting of epoxide,isocyanate, carbodiimide, N-methylol, oxazoline, silane, and mixturesthereof.
 4. The ink of claim 3, wherein Z¹ is a polyol substituted withthe aqueous dispersing moiety.
 5. The ink of claim 4, wherein Z² is apolyol substituted with one or more cross-linkable moieties.
 6. The inkof claim 5, wherein the aqueous dispersing moiety consists of one ormore carboxyl groups.
 7. The ink of claim 6, wherein the cross-linkablemoiety consists of one or more carboxyl groups.
 8. The ink of claim 7,wherein Y is NR⁴.
 9. The ink of claim 8, wherein the polymeric binder ispolyurethane.
 10. The ink of claim 3, wherein X is OH.
 11. The ink ofclaim 10, wherein Z¹ is a polyol substituted with the aqueous dispersingmoiety.
 12. The ink of claim 11, wherein Z² is a polyol substituted withone or more cross-linkable moieties.
 13. The ink of claim 12, whereinthe polymeric binder is polyurethane.
 14. The ink of claim 3, wherein Xis NHR⁴.
 15. The ink of claim 14, wherein Z¹ is a polyol substitutedwith the aqueous dispersing moiety.
 16. The ink of claim 15, wherein Z²is a polyol substituted with one or more cross-linkable moieties. 17.(canceled)
 18. (canceled)
 19. (canceled)
 20. (canceled)
 21. (canceled)22. The ink of claim 3, wherein R⁴ is —R³—X and the polymeric binder ispolyurethane.
 23. The ink of claim 22, wherein each W is O.
 24. The inkof claim 22, wherein each W is N.
 25. The ink of claim 3, wherein themole ratio of the cross-linkable moiety to the cross-linking agent isfrom 15:1 to 1:1.5.